Process for the removal of sulfur oxide from waste gas

ABSTRACT

A process, in which sulfur dioxide gas contained in waste gas is removed therefrom and collected as gypsum. In said process, the waste gas is subjected to a flow of detergent solution of basic aluminium sulfate so that the sulfur dioxide is absorbed into the solution. This solution, now containing the sulfur dioxide, is thereafter subjected to oxidation, resulting in a decrease in the basicity thereof. The solution is then neutralized by calcium carbonate or calcium hydroxide, whereby gypsum is precipitated in the solution and collected therefrom and whereby the crude content of the solution is recovered so that it may be used again as a detergent for the waste gas.

This invention relates to a new desulfurization process of stack orwaste gas, by which sulfur dioxide gas within the stack gas iseliminated therefrom and converted into gypsum.

When various kind of desulfurization processes are classified to twocategories, viz., the so-called "wet process" and "dry process", thepresent process belongs to the "wet process". As a scrubbing ordetergent solution, a solution of basic aluminum sulfate of a suitableconcentration is contacted countercurrently the flow of stack gas, andabsorbs sulfur dioxide gas. The sulfite ion in the solution is oxidizedinto sulfate ion by blowing air succeedingly into an oxidizing towercontaining the solution, which decreases the basicity of the basicaluminum sulfate solution. By the succeeding neutralization of saidsolution by means of calcium carbonate or calcium hydroxide, gypsum isprecipitated from the solution, and simultaneously the crude content ofbasic aluminum sulfate solution is recovered and reused by recirculationas the scrubbing solution. In this case, the addition of a small amountof manganese salt into the scrubbing solution accelerates the oxidationof the sulfite ion to sulfate ion by oxygen within the stack gas in aabsorbing tower simultaneously with the absorption of sulfur dioxideinto the solution. By virtue of this oxidation within the absorbingtower, the necessity of the oxidation within the succeeding oxidationtower by air blowing is decreased which allows the use of a more compactoxidation tower. This feature is also a part of this invention.

It is well known that the basic aluminum sulfate solution absorbs muchmore sulfur dioxide gas at a lower temperature. This good absorption hasbeen utilized to absorb dilute sulfur dioxide from a stack gas at alower temperature and to desorb the gas at a high concentration at ahigh temperature.

For instance, the ICI process utilizes this characteristic of basicaluminum sulfate which absorbs sulfur dioxide into the solution at alower temperature, and then desorbs it as high concentration of SO₂ athigher temperature, which is then fed to adjacent sulfuric acid plantsas crude gas. Such plants as mentioned above were operated for someyears in Japan and England at about 40 years ago. As mentioned above,the good SO₂ absorbing ability of basic aluminum sulfate solution iswell known. Our invention partly utilizes this fact and relates to anovel combination to make the SO₂ into gypsum crystals.

In the accompanying drawing:

FIG. 1 is a flowsheet of the desulfurization process of this invention;and

FIG. 2 is a schematic diagram of the present invention.

The process flowsheet of this invention is shown in FIG. 1. Basicaluminum sulfate solution as SO₂ absorbent is made up from aluminumsulfate solution by adding powdery calcium carbonate, and fixing thesulfate ion as precipitated gypsum. One example of a suitableconcentration is Al₂ O₃ 5g/100cm³, (Al₂ O₃): (SO₃) = 10 : 16 by molarratio. Of Course, the aluminum concentration and basicity of thescrubbing solution depend on the gas condition. In most cases 0.05 - 1mol/l aluminum sulfate concentration and 0-60% basicity are used in thescrubbing solution.

This scrubbing solution is contacted countercurrently with dilute sulfurdioxide gas within an absorbing tower, and absorbs SO₂ as described inthe following Eq. (1), resulting in the production of aluminum sulfitewithin the solution. And then, in the succeeding oxidation step thescrubbing solution is oxidized by air blowing as described in thefollowing Eq. (2).

    Al.sub.2 (SO.sub.4).sub.3 Al.sub.2 O.sub.3 +  3SO.sub.2 → Al.sub.2 (SO.sub.4).sub.3 + Al.sub.2 (SO.sub.3).sub.2              Eq. (1)

    Al.sub.2 (SO.sub.3).sub.3 + 3/2 O.sub.2 → Al.sub.2 (SO.sub.4).sub.3 Eq. (2)

In this case, a small amount of manganese salt addition results in thesimultaneous oxidation of the sulfite ion within the absorbing towerwith aid of the manganese catalytic action, and lessens the necessity ofthe oxidation by air blowing in the succeeding oxidation step. Usually,the added amount of manganese salt is chosen to be about 20 g/l.

After the oxidation, the solution is neutralized by the addition ofcalcium carbonate or calcium hydroxide, and is converted to precipitatedgypsum, reviving the crude composition of the scrubbing solution with asuitable basicity of aluminum sulfate for recirculation, as shown in thefollowing Eq. (3).

    2Al.sub.2 (SO.sub.4).sub.3 + 3CaCO.sub.3 → Al.sub.2 (SO.sub.4).sub.3.Al.sub.2 O.sub.3 + 3CaSO.sub.4.2H.sub.2 O + 3CO.sub.2 Eq. (3)

As mentioned above, this novel invention is summarized as follows: Withthe combination of superior sulfur dioxide absorbing ability of thebasic aluminum sulfate aqueous solution, the sulfur dioxide within stackgas is absorbed into the scrubbing solution, and oxidized into basicaluminum sulfate, and then converted into precipitated gypsum byneutralization with calcium carbonate or calcium hydroxide, therebyrenewing with crude composition of the scrubbing solution forrecirculation with a suitable basicity of aluminum sulfate solution.

Moreover, the addition of a small amount of manganese salt to the basicaluminum sulfate solution produces an oxidation reaction in theabsorbing tower by the catalytic action of the manganese ion, andlessens the necessity of oxidation by air blowing within the oxidationtower. This can result in making the oxidation unnecessary or at leastallow it to be reduced in size supplemental characteristics of thisinvention.

FIG. 2 shows an engineering flowsheet of the present process. Stack gascontaining sulfur dioxide flows into a scrubbing tower (1), and iscontacted countercurrently with the scrubbing solution having basicaluminum sulfate and a manganese salt dissolved therein. Sulfur dioxidegas is absorbed into the solution as aluminum sulfate and aluminumsulfite. The scrubbing solution is then oxidized by air blowing withinan oxidation tower (3) for converting the sulfite ion into sulfate ion,and is neutralized within a neutralizing tank (4) by calcium carbonateand calcium hydroxide, for producing precipitated gypsum crystal andrenewing the crude composition of the scrubbing solution forrecirculation. The concentration of basic aluminum sulfate within thescrubbing solutions is suitably chosen from a wide range of basicityvalues and aluminum concentrations according to the condition of stackgas. In most cases, 0.05-1 mol/l aluminum sulfate concentration and0-60% basicity are the conditions of the scrubbing solution. As notedabove, a small amount of manganese salt is added into the scrubbingsolution. As higher manganese salt addition results in greater catalyticoxidation action, a suitable manganese concentration is chosen dependingon each condition. Usually 20 g/l of manganese concentration is regardedas suitable. The oxidation reaction occurs both within the scrubbingtower and the oxidation tower, but almost all of the oxidation reactionoccurs within the oxidation tower when no manganese salt is added.

EXAMPLE 1

Stack gas with 1.5% SO₂ concentration is passed at the speed of 15 l/mininto a packed scrubbing tower with a packed height of 30 cm and diameterof 5 cm. Scrubbing solution with concentration of Al₂ (SO₄)₃.Al₂ O₃ 270g/l and basicity of 20% is sprayed in counterflow with a feed rate of100 cm³ /min. and absorbs SO₂ from the stack gas, and then is oxidizedwithin the oxidation tank by air blowing, and neutralized by calciumcarbonate to precipitate gypsum crystal which are filtered bycentrifugal separator. As the filtrate has been neutralized to thebasicity similar to the crude scrubbing solution. The filtrate is reusedas the recycling scrubbing solution. The result of continuous operationfor 8 hours shows an average SO₂ absorbing ratio of 87% and producessuperior quality gypsum crystal. Analysis of gypsum obtained:CaO-31.84%, SO₃ -46.60%, Al-0.07%, Mn-Tr.

EXAMPLE 2

With the same equipment and the same concentration of scrubbing solutionas Example 1, stack gas with 1.5% SO₂ is passed through the tower at afeed rate of 15 l/min, and contacted with the scrubbing solution flowingdownward at the feed rate of 200 cm³ /min. The result of 9 hours'continueous operation shows an average SO₂ absorbing ratio of 95.5%, andproduces a superior quality gypsum crystal. Analysis of gypsum obtained:CaO-32.80%, SO₃ -46.65%, Al-0.05%.

EXAMPLE 3

With the same equipment as described above, at a feed rate of 15 l/min,stack gas with 0.5% SO₂ content is washed with the same content ofscrubbing solution flowing with a feed rate of 100 cm³ /min. The resultof 9 hours' continueous operation shows an average SO₂ absorbing ratioof 95.5%, and produces superior quality gypsum crystal. Analysis ofgypsum obtained: CaO-32.34%, SO₃ -46.43%, Al-0.05%.

EXAMPLE 4

With the same equipment as described above, at a feed rate of 15 l/min.stack as with 0.5% SO₂ content is scrubbed by a scrubbing solutionflowing with a feed rate of 100 cm³ /min. which contains 270 g/l of Al₂(SO₄)₃.Al₂ O₃ and a basicity of 20% and Example 4 also containing 20 g/lof MnSO₄. The result of 8 hours continuous operation shows an averageSO₂ absorbing ratio of 96.0%, and an oxidation ratio of 50.0% within theabsorbing packed tower.

With oxidation by air blowing within the succeeding oxidation tower, thesulfite ion is completely oxidized into sulfate ion. The time requiredfor this oxidation is about half of the time required for the oxidationwithout MnSO₄. The solution is then neutralized within the neutralizingtank by calcium carbonate to convert the sulfate ion into precipitatedgypsum, and filtrated by a centrifugal separator. After the filtrate isneutralized to the same basicity of the crude scrubbing solution, thefiltrate is circulated again as a scrubbing solution.

EXAMPLE 5

3,500 Nm³ /Hr stack gas with 0.65% SO₂ is contacted countercurrentlywith 0.3 mol/l of basic aluminum sulfate solution flowing downward at afeed rate of 20 m³ M, controlling the basicity by neutralization ofcalcium carbonate for recirculation. The average SO₂ absorbing ratio hasover 90%, and superior quality of gypsum was obtained.

What is claimed is:
 1. A process for removing sulfur oxide from wastegas which comprisesa. subjecting the waste gas to a countercurrent flowof an absorbent solution of 0.05 to 1 mol/liter of basic aluminumsulfate, said solution having a basicity of 0 to 60%, and containing.Iadd.about .Iaddend.20 g/l of a manganese salt to absorb the sulfuroxide into the solution and oxidize the absorbed sulfur oxide by meansof the manganese salt; and b. blowing air through the absorbent solutionfrom step a) to oxidize sulfite ion in the solution to sulfate ion; c.neutralizing the solution from step a) by adding calcium carbonate orcalcium hydroxide whereby gypsum is precipitated; and d. separating thegypsum and reusing the solution as the absorbent solution in step a). 2.The process as claimed in claim 1, in which the precipitated crystallinegypsum is collected by filtration. .Iadd.
 3. A process for removingsulfur oxide from waste gas which comprises .Iadd.a. subjecting thewaste gas to a countercurrent flow of an absorbent solution of 0.05 to 1mol/liter of basic aluminum sulfate, said solution having a basicity of0 to 60%, and containing an amount of a manganese salt sufficient toabsorb the sulfur oxide into the solution and oxidize the absorbedsulfur oxide by means of the manganese salt; and .Iadd. b. blowing airthrough the absorbent solution from step a) to oxidize sulfite ion inthe solution to sulfate ion; .Iadd. c. neutralizing the solution fromstep a) by adding calcium carbonate or calcium hydroxide whereby gypsumis precipitated; and .Iadd. d. separating the gypsum and reusing thesolution as the absorbent solution in step a)..Iaddend.